In answer to various inquiries concerning the manufacture of this
article, we give herewith the process of William Henry Balmain, the
original discoverer of luminous paint, and also other processes. These
particulars are derived from the letters patent granted in this country
to the parties named.
Balmain's invention was patented in England in 1877, and in this country
in 1882. It is styled as Improvements in Painting, Varnishing, and
Whitewashing, of which the following is a specification:
The said invention consists in a luminous paint, the body of which is a
phosphorescent compound, or is composed in part of such a compound, and
the vehicle of which is such as is used as the vehicle in ordinary paint
compounds, viz., one which becomes dry by evaporation or oxidation.
The objector article to which such paint or varnish or wash is applied
is itself rendered visible in the darkest place, and more or less
capable of imparting light to other objects, so as to render them
visible also. The phosphorescent substance found most suitable for the
purpose is a compound obtained by simply heating together a mixture
of lime and sulphur, or carbonate of lime and sulphur, or some of the
various substances containing in themselves both lime and sulphur--such,
for example, as alabaster, gypsum, and the like--with carbon or other
agent to remove a portion of the oxygen contained in them, or by heating
lime or carbonate of lime in a gas or vapor containing sulphur.
The vehicle to be used for the luminous paint must be one which will dry
by evaporation or oxidation, in order that the paint may not become soft
or fluid by heat or be liable to be easily rubbed off by accident or use
from the articles to which it has been applied. It may be any of the
vehicles commonly used in oil-painting or any of those commonly used in
what is known as "distemper" painting or whitewashing, according to the
place or purpose in or for which the paint is to be used.
It is found the best results are obtained by mixing the phosphorescent
substance with a colorless varnish made with mastic or other resinous
body and turpentine or spirit, making the paint as thick as convenient
to apply with a brush, and with as much turpentine or spirit as can
be added without impairing the required thickness. Good results may,
however, be obtained with drying oils, spirit varnishes, gums, pastes,
sizes, and gelatine solutions of every description, the choice being
varied to meet the object in view or the nature of the article in hand.
The mode of applying the paint, varnish, or wash will also depend upon
the circumstances of the case. For example, it may be applied by a
brush, as in ordinary painting, or by dipping or steeping the article
in the paint, varnish, or wash; or a block or type may be used to
advantage, as in calico-printing and the like. For outdoor work, or
wherever the surface illuminated is exposed to the vicissitudes of
weather or to injury from mechanical contingencies, it is desirable to
cover it with glass, or, if the article will admit of it, to glaze it
over with a flux, as in enameling, or as in ordinary pottery, and this
may be accomplished without injury to the effect, even when the flux or
glaze requires a red heat for fusion.
Among other applications of the said invention which may be enumerated,
it is particularly advantageous for rendering visible clock or watch
faces and other indicators--such, for example, as compasses and the
scales of barometers or thermometers--during the night or in dark places
during the night time. In applying the invention to these and other
like purposes there may be used either phosphorescent grounds with
dark figures or dark grounds and phosphorescent figures or letters,
preferring the former. In like manner there may be produced figures and
letters for use on house-doors and ends of streets, wherever it is not
convenient or economical to have external source of light, signposts,
and signals, and names or marks to show entries to avenues or gates, and
the like.
The invention is also applicable to the illumination of railway
carriages by painting with phosphorescent paint a portion of the
interior, thus obviating the necessity for the expense and inconvenience
of the use of lamps in passing through tunnels. It may also be applied
externally as warning-lights at the front and end of trains passing
through tunnels, and in other similar cases, also to ordinary carriages,
either internally or externally. As a night-light in a bed-room or in a
room habitually dark, the application has been found quite effectual, a
very small proportion of the surface rendered phosphorescent affording
sufficient light for moving about the room, or for fixing upon and
selecting an article in the midst of a number of complicated scientific
instruments or other objects.
The invention may also be applied to private and public buildings in
cases where it would be economical and advantageous to maintain for a
short time a waning or twilight, so as to obviate the necessity for
lighting earlier the gas or other artificial light. It may also be
used in powder-mills and stores of powder, and in other cases where
combustion or heat would be a constant source of danger, and generally
for all purposes of artificial light where it is applicable.
In order to produce and maintain the phosphorescent light, full sunshine
is not necessary, but, on the contrary, is undesirable. The illumination
is best started by leaving the article or surface exposed for a short
time to ordinary daylight or even artificial light, which need not be
strong in order to make the illumination continue for many hours, even
twenty hours, without, the necessity of renewed exposure.
The advantages of the invention consist in obtaining for the purposes of
daily life a light which is maintained at no cost whatever, is free from
the defects and contingent dangers arising from combustion or heat, and
can be applied in many cases where all other sources of light would be
inconvenient or incapable of application.
Heretofore phosphorus has been mixed with earthy oxides, carbonates,
and sulphates, and with oxides and carbonates of metal, as tin, zinc,
magnesia, antimony, and chlorides of the same, also crystallized acids
and salts and mineral substances, and same have been inclosed and
exhibited in closely-stopped bottles as a phosphorus; but such union I
do not claim; but what I claim is:
A luminous paint, the body of which is a phosphorescent substance, or
composed in part of such substance, the vehicle of which is such as is
ordinarily used in paints, viz., one which will become dry by oxidation
or evaporation, substantially as herein described.
A. Krause, of Buffalo, N.Y., obtained a patent for improvement in
phosphorescent substances dated December 30, 1879. The patentee says:
This invention relates to a substance which, by exposure to direct or
indirect sun-light, or to artificial light, is so affected or brought
into such a peculiar condition that it will emit rays of light or become
luminous in the dark.
It is a well-known fact that various bodies and compositions of matter,
more especially compositions containing sulphur in combination with
earthy salts, possess the property of emitting rays of light in the
dark after having been exposed to sun-light. All of these bodies and
compositions of matter are, however, not well adapted for practical
purposes, because the light emitted by them is either too feeble to be
of any practicable utility, or because the luminous condition is not
of sufficient duration, or because the substances are decomposed by
exposure to the atmosphere.
Among the materials which have been employed with the best results
for producing these luminous compositions are sea-shells, especially
oyster-shells. I have found by practical experiments that only the inner
surface of these shells is of considerable value in the production
of luminous compositions, while the body of the shell, although
substantially of the same chemical composition, does not, to any
appreciable extent, aid in producing the desired result. It follows from
this observation that the smallest shells, which contain the largest
surface as compared with their cubic contents, will be best adapted for
this purpose.
I have found that chalk, which is composed of the shells of microscopic
animals, possesses the desired property in the highest degree; and my
invention consists, therefore, of a luminous substance composed of such
chalk, sulphur, and bismuth, as will be hereinafter fully set forth.
In preparing my improved composition I take cleaned or precipitated
chalk, and subject it to the process of calcination in a suitable
crucible over a clear coal or charcoal fire for three or four hours,
or thereabout. I then add to the calcined chalk about one-third of its
weight of sulphur, and heat the mixture for from forty-five to ninety
minutes, or thereabout. A small quantity of bismuth, in the proportion
of about one per cent, or less of the mixture, is added together with
the sulphur.
The metal may be introduced in the metallic form in the shape of
fillings, or in the form of a carbonate, sulphuret, sulphate, or
sulphide, or oxide, as may be most convenient.
The substance produced in this manner possesses the property of emitting
light in the dark in a very high degree. An exposure to light of very
short duration, sometimes but for a moment, will cause the substance
to become luminous and to remain in this luminous condition, under
favorable circumstances, for upward of twenty-four hours.
The intensity of the light emitted by this composition after exposure is
considerable, and largely greater than the light produced by any of the
substances heretofore known.
The hereinbefore described substance may be ground with oil and used
like ordinary paint; or it may be ground with any suitable varnish or be
mixed in the manner of water colors; or it may be employed in any other
suitable and well-known manner in which paints are employed.
My improved luminous substance is adapted for a great variety of
uses--for instance, for painting business and other signs, guide boards,
clock and watch dials, for making the numbers on houses and railway
cars, and for painting all surfaces which are exposed periodically to
direct or indirect light and desired to be easily seen during the night.
When applied with oil or varnish, my improved luminous substance can
be exposed to the weather in the same manner as ordinary paint without
suffering any diminution of its luminous property. I claim as my
invention the herein described luminous substance, consisting of
calcined chalk, sulphur, and bismuth, substantially as set forth.
Merrill B. Sherwood, Jr., of Buffalo, N. Y., obtained a patent for a
phosphorescent composition, dated August 9, 1881.
The author says: My invention relates to an improvement in
phosphorescent illuminants.
I have taken advantage of the peculiar property which obtains in many
bodies of absorbing light during the day and emitting it during the
night time.
The object of my invention is the preparation by a prescribed formula,
to be hereinafter given, of a composition embodying one of the
well-known phosphorescent substances above referred to, which will be
applicable to many practical uses.
With this end in view my invention consists in a phosphorescent
composition in which the chief illuminating element is monosulphide of
calcium.
The composition obtained by the formula may be used either in a powdered
condition by dusting it over articles previously coated, in whole or in
part, with an adhesive substance, or it may be intimately mixed with
paints, inks, or varnishes, serving as vehicles for its application, and
in this way be applied to bodies to render them luminous.
The formula for obtaining the composition is as follows: To one hundred
parts of unslaked lime, that obtained from calcined oyster shells
producing the best results, add five parts of carbonate of magnesia and
five parts of ground silex. Introduce these elements into a graphite or
fire-clay crucible containing forty parts of sulphur and twenty-five
parts of charcoal, raise the whole mass nearly or quite to a white heat,
remove from the fire, allow it to cool slowly, and, when it is cold or
sufficiently lowered in temperature to be conveniently handled,
remove it from the crucible and grind it. The method of reducing the
composition will depend upon the mode of its use. If it is to be applied
as a loose powder by the dusting process, it should be simply ground
dry; but if it is to be mixed with paint or other similar substance,
it should be ground with linseed or other suitable oil. In heating the
elements aforesaid, certain chemical combinations will have taken place,
and monosulphide of calcium, combined with carbonate of lime, magnesia,
and silex, will be the result of such ignition.
If, in the firing of the elements, as above set forth, all of the
charcoal does not unite with the other elements, such uncombined portion
should be removed from the fused mass before it is ground.
If it is designed to mix the composition with paints, those composed of
zinc-white and baryta should be chosen in preference to those composed
of white lead and colored by vegetable matter, as chemical action will
take place between the composition and paint last mentioned, and
its color will be destroyed or changed by the gradual action of the
sulphureted hydrogen produced. However, by the addition of a weak
solution of gum in alcohol or other suitable sizing to the composition,
it may be used with paints containing elements sensitive to sulphureted
hydrogen without danger of decomposing them and destroying their color.
In many, and possibly in a majority of cases, the illuminating
composition applied as a dry powder will give the most satisfactory
results, in view of the tendency to chemical action between the paint
and composition when intimately mixed; in view of the fact that by
the addition to paint of any color of a sufficient quantity of the
composition to render the product luminous, the original color of the
paint will be modified or destroyed; and, also, in view of the fact that
the illuminating composition is so greatly in excess of the paint, the
proportions in which they are united being substantially ten parts
of the former to one of the latter, it will be difficult to impart a
particular color to the product of the union without detracting from
its luminosity. On the other hand, the union of dry powder with a body
already painted by the simple force of adhesion does not establish
a sufficiently intimate relation between it and the paint to cause
chemical action, the application of a light coat of powder does not
materially change the color of the article to which it is applied; and,
further, by the use of the powder in an uncombined state its greatest
illuminating effects are obtained. Again, if the appearance in the
daytime of the article which it is desired to have appear luminous at
night is not material, it may be left unpainted and simply sized to
retain the powder.
In printing it is probable that the composition will be employed almost
exclusively in the form of dry powder, as printing-ink, normally pasty,
becomes too thick to be well handled when it is combined with powder in
sufficient quantity to render the printed surface luminous. However, the
printed surface of a freshly printed sheet may be rendered luminous by
dusting the sheet with powder, which will adhere to all of the inked and
may be easily shaken from the unmoistened surfaces thereof.
I am aware that monosulphide of calcium and magnesia have before
been used together in phosphorescent compounds. What I claim is a
phosphorescent composition consisting of monosulphide of calcium,
combined with carbonate of lime, magnesia, and silex, substantially as
described.
Orlando Thowless, of Newark, N.J., obtained a patent for a process of
manufacturing phosphorescent substances dated November 8, 1881.
The inventor says: The object of my invention is to manufacture
phosphorescent materials of intense luminosity at low cost and little
loss of materials.
I first take clam shells and, after cleaning, place them in a solution
composed of about one part of commercial nitric acid and three parts of
water, in which the shells are allowed to remain about twenty minutes.
The shells are then to be well rinsed in water, placed in a crucible,
and heated to a red heat for about four hours. They are then removed and
placed, while still red-hot, in a saturated solution of sea salt, from
which they are immediately removed and dried. After this treatment and
exposure to light the shells will have a blood-red luminous appearance
in the dark. The shells thus prepared are used with sulphur and
the phosphide and sulphide of calcium to produce a phosphorescent
composition, as follows: One hundred parts, by weight, of the shells,
prepared as above, are intimately mixed with twenty parts, by weight, of
sulphur. This mixture is placed in a crucible or retort and heated to a
white heat for four or five hours, when it is to be removed and forty
parts more of sulphur, one and one-half parts of calcium phosphide, and
one-half part of chemically pure sulphide of calcium added. The mixture
is then heated for about ninety minutes to an extreme white heat. When
cold, and after exposure to light, this mixture will become luminous.
Instead of these two ignitions, the same object may be in a measure
accomplished by the addition of the full amount of sulphur with the
phosphide and sulphide of calcium and raising it to a white heat but
once. The calcium phosphide is prepared by igniting phosphorus in
connection with newly slaked lime made chemically pure by calcination.
The condition of the shells when the sulphur is added is not material;
but the heat renders them porous and without moisture, so that they will
absorb the salt to as great an extent as possible. Where calcined shells
are mixed with solid salt, the absorbing power of the shells is greatly
diminished by the necessary exposure, and there will be a lack of
uniformity in the saturation. On the contrary, by plunging the red-hot
shells in the saline solution the greatest uniformity is attained.
Instead of using clam shells as the base of my improved composition, I
may use other forms of sea shells--such as oyster shells, etc.